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CONTENTS
Page
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1. INTRODUCTION
Isoprene (2-methyl-l,3-butadiene) has been for many years a substance of very considerable interest in the study of rubber, since it
has been shown to be the fundamental unit in the constitution of the
rubber hydrocarbon. Isoprene polymerizes to form a product which
1
Guest worker at the National Bureau of Standards from -Lhe Polytechnic Institute, Warsaw, Poland.
106351-36--6
883
884
[Vol. 17
'1
Bekkedahl, WOod,]
Wojciechowski
885
\'
A number of previous observers have noted that isoprene on standing for months or years at room temperature under atmospheric
conditions will oxidize and polymerize [1, 11, 12, 26, 44, 55]. For
this reason the physical properties here reported were determined as
soon as possible after the final distillation. With the exception of
the freezing point and expansivity, all measurements were made
within 5 hours after the end of the final distillation. The sample used
in the freezing-point determination had been kept in a refrigerator at
about 8 C for 2 days, while that used in determining the expansion
was several weeks old.
The expansivity, however, is thought to change only slightly with
change in purity. In order to obtain some idea of the rate of polymerization, a sample which had been kept at 8 C for 2 months was
distilled, and a solid residue amounting to less than 0.5 percent of
the weight of the sample was obtained.
1. DEGREE OF PURITY
scale for the degree of purity of liquids. This scale is based on the
measurement of t:"t, the difference between the temperature of the
boiling liquid and the temperature of the condensing vapor as determined in a differential ebulliometer of standard dimensions. For a
pure substance t:"t is zero, and increases with increased concentration
of impurities.
The freshly prepared sample of isoprene from the third distillation
was found to have a t:"t of 0.002 C. This value falls within the limits
of the fifth or highest degree on the purity scale (range from 0.000 to
0.005 C). A sample of isoprene from the previous distillation was
found to have a t:"t of 0.006 C. Its purity then was of the fourth
degree (range from 0.005 to 0.020 C). This sample was left in the
ebulliometer at room temperature for 2 weeks. At the end of this
time its t:"t value had increased to 0.028 C, and its purity had decreased
to the third degree (range from 0.020 to 0.050 C). This increase
in M is direct confirmation of the expected decrease in purity brought
about by oxidation and polymerization of the isoprene. Changes with
time in other physical properties as mentioned below are other evidences of change in the material.
886
[Vol. 17
The normal boiling point of isoprene was determined in the ebulliometer used for the purity determination, following the comparative method of Swi~toslawski [43]. According to this procedure a
second ebulliometer containing pure boiling water is connected,
together with the first ebulliometer, to a closed system in which the
pressure can be adjusted. Determinations of the boiling point, by
observing the temperature of the boiling liquid in equilibrium with
the vapor, were made for both liquids under at least three different
pressures, including values both above and below 760 mm of mercury. The temperatures were measured with a Mueller [31] type
of Wheatstone bridge and a resistance thermometer designed for
precise temperature measurements [29], and calibrated in accordance
with the procedure for the International Temperature Scale [10].
In order to obtain the normal boiling point of isoprene from the
observations it was merely necessary to find the boiling point of isoprene under the pressure at which the boiling point of water would be
exactly 100 0, since that pressure is exactly 760 mm by definition of
the temperature scale. This procedure avoids the loss of precision
inherent in the corrections to be applied to the readings of a mercury
barometer.
For a sufficiently small range of pressures near the normal boiling
points the relation between t s , the boiling point of an organic substance, and tID, the boiling point of water under the same pressure,
can be represented by a function of the second degree; hence its
derivative, ::;, changes linearly with change of pressure when this
pressure is defined by the boiling point of water [58].
It was found
t' '" and tw, and til", and t"" respectively; tw being a measurement
close to 760 mm pressure, t' w below, and til w above this pressure.
The derivative ::; at 100.000 0 was obtained by interpolation.
These values are given in table 1. The normal boiling point, tn, is
then calculated [57] from the observed values of ts and tw by the
equation
Bekkedah/, WoOd,]
Wojciechowski
887
T ABLE I.-Degree of purity, boiling point, and change of boiling point with change
of pressure for several samples of isopTene
Degree of purity
de,"
dt",
Boiling
point of
water
(~ ) .
dP ,
Normal
boiling
point of
isoprene
sample
- - - - - - - -- -1---- - -- - -- - -0
0.028
.006
.002
O/mm
34. 124
34.102
34.076
Difference between the boiling temperature of isoprene and its condensation temperatnre in a differen
t ial ebulliometer of standard dimensions .
Ratio of the change in boiling pOint of isoprene to that of water for tbe same change in pressure.
Ohange of boiling point of isoprene per m illimeter change of pressure at 760 mm.
d At mid point between t, and t', .
e t"II/+t ..
-2-'
f
g
h
i
Interpolated value.
Defining 760 mm pressure.
At midpoint betwoen t', and t,.
t'lI'+tw
-2- '
dt
The value of dP' the change of boiling point of isoprene with
change of pressure at 760 mm of mercury, was obtained by multiplying the value of the derivative
:t~
the value in degrees per millimeter for the change of boiling point of
water at 760 mm [32]. The value for isoprene was thus found to be
0.0382 0 per millimeter of mercury.
Table 1 also shows the data and results of these determinations.
For the purpose of comparison some values are also given for samples
of lower purity.
t~
are
888
[Vol. 17
- 143
o~
\
\\
-/44
'" - /45
Q:
I
II
"'\
,<:,
~ -146
a" I~J.
II
---
"
-141
. /-/46.85
__ COOLING "
WARMING
-V
><0-
-- -
-148
10
20
"30
40
TIME:
FIGURE
50
-
60
10
90
80
100
MINUTES
.I
"-
8
'" .0012
j..-O-O"
.-[p---
t
I
)
...;
~ .0010
-/50
-125
-/00
-so
TEMPERA'TURE
FIGURE
-25
25
so
"c
temperatures neal' the freezing point almost to the boiling point. The
dilatometer, made of low-expansivity glass, had a bulb with a volume
of 22.31 ml capacity, joined to a capillary about 40 cm in length with
an average volume of 0.02276 ml per centimeter. A temperature
range of about 20 C was covered in each run. For each run there
was plotted a graph of the height of the liquid in the capillary as a
B ekkedahl, WOOd, ]
Wojciechowski
889
~ ~~ = -
890
[Vol .n
values for density and expansivity, 1.5 ml/gj and t~, the rate of change
of boiling point with change of pressure as previously measured,
0.0382 C per millimeter (or 28.7XlO- 6 C per dyne/cm 2 ). The
latent heat of vaporization of isoprene at the normal boiling point is
thus calculated to be 380 jig (90.8 cal/g) or 25.9 kj/mole (6.17
kcal/mole). Because of the uncertainty in the value of the specific
volume of the vapor the estimated probable error in the calculation
is 1 percent.
The Bingham-Nernst modification [6] of Trouton's rule is
~:= 17+0.011TB'
in which Lm is the molal latent heat of vaporization in calories, and
TB the absolute temperature of the boiling point. The right-hand
member of the equation has the value 20.4, and the left-hand member
20.1. The rule in this form appears to be valid for isoprene within the
limits of precision of determination of the heat of vaporization. This
is taken as evidence that isoprene in the liquid form is not associated.
7. REFRACTIVE INDEX AND MOLECULAR REFRACTION
j
~
Bekkedah/, WOOd,]
Wojciechowski
891
-0.656XIO-3 per degree centigmde. Therefore, the index of refraction, nD, at temperature, t, is
nD= 1.43472-0.656X 1O-3t.
This equation is applicable for liquid isoprene at least over the range
from 9 to 30
and probably over a wider range. The refractive
indices of fractions boiling both below and immediately above the
purest isoprene were lower than that of the isoprene. The property
is, however, not sensitive to very small amounts of impurities having
boiling points neal' that of isoprene, since the third distillation, which
lowered f:"t from 0.006 to 0.002 0, raised the refractive~_index only by
about 0.00001.
~
<:;. Oxidation and polymerization of the"isoprene on standing, however,
brought: about progressive increases)n:refractive index. }~ For the first
1.4.10
1.4-28
.~
1.42 6
1.42 4
""
i::
1.420
-~
"~
"-
~ 1.418
~~
1.41 6
1.414
10
12
14
Iii
18
20
TeMPeRATURe
FIGURE
22
24
26
28
~
.10
few days the daily changes were of the order of 0.0002. Later the rate
of increase became considerably less, and rather variable. At the end
of 2 months the total increase was about 0.00450, and the material
had become so lacking in homogeneity that further measurements
were impossible.
The molecular refraction is often calculated by summing up the
refractions of the individual atoms and adding a certain quantity for
the "exaltation" due to double bonds or other special features of the
structure. In the present case, however, no precise calculation is
possible because the exaltation due to the conjugated double bond
varies considerably from one compound to another. From the
Lorenz-Lorentz formula, using the refractive index and density values
as determined in this investigation, the molecular refraction is computed to be 25.39. By taking this value for the molecular refraction,
and 2,490 and 1.066 for the atomic refractions of carbon and hydrogen,
respectively, as reported by Swi<;ltoslawski [38], the exaltation due to the conjugated system in isoprene is 4.41. This is not greatly different
892
[Vol. 17
The boiling point, density, and refractive index of isoprene have been
determined by many investigators, and the more significant results
are given in table 2. For the purpose of comparison, the boiling
points have been converted, wherever possible, to those at 760 mm
pressure. Also the original values of density and refractive index have
been converted to those at 20 C.
TABLE
Year
ence
num-
Boiling point
at71lOmm
ber
[56J
[47]
[18J
[451
[46
1860
1882
1886
1893
1894
1895
1897
1897
1906
1911
[34J
[24J
[16]
[7]
[22J
1911
[21J
1913
1913
1914
1914
1915
1916
[26]
[25J
[19J
[37J
[2]
[15J
1916
1929
1930
1931
1931
1932
1936
[14J
[52J
[l1J
[23J
[17J
[55J
Density
at 20
glml
Refrac-
tive index at
20 0
Freezing
point
g~-tO-37~~::::::::
:~m
:::::::::: :::::::::::
32 to 33_________
. 6722
1. 40646 __________ _
33 to 39" __ __ __________________________________ _
30 ___________________________ ______ __________ _
35 to 37____ ____ __________________________ ____ _
30 to 37_________
.676
1.41205 ___ _______ _
{36 t o 37____ _____
.6800
1. 42333 __________ _
35.5 to 36.0______
.6803
1.42019 __________ _
34.5 to 35.0_ _ ____
.6803
1. 42207 _______ ___ _
__________________
.6803 __________ __________ _
33.7 to 33.9______
.6832
1. 42387 ___ ____ ___ _
33.5 to 34.0"__ ___
.6760 ___ ___________ __ ____ _
34.1 to 34.6_ ____ _
.6811
1. 41540 __________ _
__ __________ ______________________ ___ "About
-120 0"
33.9 to34.4___ ___
.6809
1.41786 __ ___ ____ __
34.4 to 34.9______
.6806
1. 4194 ______ ____ _
36 to 38_________
.68
____________ ________ _
33.7 to 34.1. __ _______ _________________ ________ _
34.4 to 35.8__ ____
.6828
1.42093 ___ ___ ____ _
34.0 to 34.5 __ _____ _____ _________ ______________ _
.6805
1.42160
-146.8
34.076___ ______ __
Bekkedahl, WoOd, ]
Wojciechowski
893
[1)
[2]
[3]
[4]
[5]
[6]
(7)
(8)
[9]
[10]
[11]
[12]
[13]
[14]
[15)
, Mieczyslaw Wojciechowski.
894
IVol.17
[16] Euler, J. prakt. Chern. [2] 57, 131 (1898). Ber. deut. chern. Ges. 30, 1989
(1897).
[17] Farmer and Warren, J. Chern. Soc. 1931, p. 3221.
[18] Gladstone, J. Chern. Soc. <19, 609 (1886).
[19] Harries, Ber. deut. chern. Ges. <l7B, 1999 (1914).
[20] Harries, Ber. deut. chern. Ges. 35, 3256 (1902).
[21] Harries, Ann. Chern. 383, 157 (1911) .
[22] Harries and Gottlob, Ann. Chern. 383, 228 (1911).
[23] Heisig, J. Am. Chern. Soc. 53, 3245 (1931).
[24] Ipatiew, J. prakt. Chern. [2]i 55, 41(1897) .
[25] Kucherow, J . Russ. Phys. Chern. Soc. <15, 1634 (1913).
[26] Lebedew and Skawronski, J. Russ. Phys. Chern. Soc. <15, 1296 (1913); Bul.
soc. chim. 16, 80 (1914); J. Soc. Chern. Ind. 33, 1224 (1914).
[27] Lewis, Ind. Eng. Chern. 28,257 (1936) .
[28] M air, BS J. R esearch 9, 457 (1932) RP482.
[29] M eyers, BS J. Research 9, 807 (1932) RP508.
[30] Midgley and Henne, J. Am. Chern. Soc. 51, 1216 (1929). Reprinted in
Rubber Chern. Tech. 2, 441 (1929).
[31] Mueller, Bul. BS 13, 547 (1916) S288.
[32] Osborne and Meyers, J. Research NBS 13, 1 (1934) RP691.
[33] Ostromysslenski, Chern. Zentr. 87, I, 973, 1068 (1916).
[34] Perkin, J. Chern. Soc. 67, 255 (1895).
[35] Pickles, J. Chern. Soc. 97, 1085 (1910).
[36] Smith and Wojciechowski, Roczniki Chern. 16, 104 (1936). Bul. into acado
polonaise [A] (March 1936) (in English).
[37] Steimmig, Ber. deut. chern. Ges. <l7A, 852 (1914).
[38] Swi~toslawski , J . Am. Chern. Soc. <12, 1945 (1920).
[39] Swi~toslawski, J. chim. phys. 27,329 (1930). Bul. soc. chim. [4] <19, 1563
(1931) .
[40] Swi~toslawski, Ebuljometrja, Kasy im Mianowskiego, Warszawa (1935).
Ebulliometry, Memoires de l' Academie Polonaise des Sciences et des
Lettres [A] no. 3 (1936), Jagellonian University Press, Krakow (in English).
[41] Swi~toslawski, Roczniki Chern. 11, 545 (1931).
[42] Swi~toslawski, IX Congreso into Quim. Pura Aplicada Madrid, 2, 81 (1934) .
Bul. into acado polonaise [A] 504 (1930); 177 (1933). Compt. rend. 192,
1457 (1931). Roczniki Chern. 13, 176, 227 (1933). Chern. Listy 26,
442 (1932). J. Phys. Chern. 38, 1169 (1934).
[43] Swi~toslawski, J. Phys. Chern. 27, 496 (1930).
[44] Thomas and Carmody, J. Am. Chern. Soc. 5<1, 2480 (1932); 55, 3854 (1933).
[45] Thorpe and Jones, J. Chern. Soc. 63, 273 (1893).
[46] Thorpe and Rodger, Trans. Roy. Soc. 185A, 397 (1894).
[47] Tilden, Chern. News <16, 120 (1882). J. Chern. Soc. <15, 410 (1884) .
[48] Tilden, Chern. News 65,265 (1892).
[49] Wallach, Ann. Chern. 238, 78 (1887).
[50] Wallach, Ber. deut. chern. Ges. 2<1, 1525 (1891).
[51] Washburn and Smith, BS J. Research 12, 305 (1934) RP656.
[52] Waterman and van Westen, Rec. trav. chim. <18, 1084 (1929).
[53] Weber, J. Soc. Chern. Ind. 13, 11 (1894).
[54] Weber, Ber. deut. chern. Ges. 33, 779 (1900).
[55] Whitby and Crozier, Can. J. Research 6, 203 (1932). Reprinted in Rubber
Chern. Tech. 5, 546 (1932).
[56] Williams, Proc. Roy. Soc. 10, 516 (1860). Jahresber. 1860, p. 494. Chern.
News 2, 206 (1860). Trans. Roy. Soc. 1860, p. 241. Phil. Mag. [4] 21,
463 (1861).
[57] Wojciechowski, J. Research NBS 17, 453 (1936) RP921.
[58] Zmaczynski, J. chim. phys. 27, 503 (1930). Roczniki Chern. 13, 181 (1933).